Três novas supermoléculas, aqui designadas por ZnTCP4+, MnTCP5+ e CoTCP5+, foram obtidas pela coordenação de quatro acetatos trinucleares assimétricos de rutênio, [Ru3O(CH3CO2)6(py)2(CH3OH)]+, aos resíduos piridínicos de meso-tetra(4-piridil)porfirinato de ZnII, MnIII e CoIII, respectivamente (ZnTPyP, MnTPyP e CoTPyP). A caracterização destas supermoléculas foi efetuada por espectroscopia de ressonância magnética nuclear e espectroscopia eletrônica. O comportamento eletroquímico foi investigado por voltametria cíclica e espectroeletroquímica. Os efeitos dos acetatos trinucleares periféricos sobre a reatividade do núcleo porfirínico foram analisados: (i) para ZnTCP4+, além da supressão da luminescência, verificou-se que as constantes de coordenação axial determinadas em diclorometano para piridina e imidazol, quando comparadas às respectivas constantes de ZnTPyP e de meso-tetra(fenil)porfirinato de zinco, indicaram um aumento significativo da acidez de Lewis do íon Zn2+; (ii) MnTCP5+ revelou-se um catalisador mais seletivo que MnTPyP na oxidação de ciclohexano em fase homogênea, utilizando-se iodosilbenzeno como doador de oxigênio; (iii) os eletrodos modificados por filmes de CoTCP5+ apresentaram uma eficiente atividade catalítica na redução tetra-eletrônica de dioxigênio a água, comportamento que contrasta com o descrito na literatura para filmes de CoTPyP. A redução tetra-eletrônica de dioxigênio catalisada pelos filmes de CoTCP5+ foi confirmada por voltametria cíclica, voltametria de eletrodo disco rotatório e voltametria de eletrodo de anel e disco rotatórios. / Three novel supermolecules designated as ZnTCP4+, MnTCP5+, and CoTCP5+ were obtained by coordination of four assymetric trinuclear ruthenium acetate species, [Ru3O(CH3CO2)6(py)2(CH3OH)]+ to pyridine residues of ZnII -, MnIII -, and CoIIITPyP, respectively (TPyP = meso-tetra(4-pyridil)porphyrinate). These new compounds were characterized by nuclear magnetic resonance spectroscopy and electronic spectroscopy. The electrochemical behavior was investigated by cyclic voltammetry, and spectroelectrochemistry. The influence of the peripheral trinuclear acetate on the porphyrin core reactivity was assayed: (i) for ZnTCP4+, besides the luminescence quenching, the calculated equilibrium constants for axial coordination of pyridine and imidazole in dichloromethane demonstrated a significant increase in the Zn2+ Lewis acidity in comparison with the respective constants from ZnTPyP and zinc meso-tetra(phenyl)porphyrinate; (ii) MnTCP5+ exhibited improved selectivity as catalyst for ciclohexane oxidation (homogeneous phase) in comparison with MnTPyP using iodosylbenzene as oxygen donor; (iii) modified electrodes by CoTCP5+ films showed an outstanding catalytic activity in the tetraelectronic reduction of dioxygen to water, in contrast with CoTPyP films described in the literature; the dioxygen tetraelectronic reduction was confirmed by cyclic voltammetry, rotating disk electrode voltammetry, and rotating ring and disk electrode voltammetry.

In ariden Gebieten tritt Schwefelwasserstoff häufig im Grundwasser auf, wodurch dessen Nutzung für die Trinkwassergewinnung aufgrund des störenden Geruchs und Geschmacks stark beeinträchtigt wird. Die in der Praxis oft eingesetzte Belüftung erweist sich zumeist als ineffizient und führt zu Geruchsbelästigungen in der Umgebungsluft. Das Ziel der Arbeit, die im Rahmen eines deutsch-israelischen Forschungsprojekts angefertigt wurde, bestand darin, einen wirksamen und für den praktischen Einsatz bei der Wasseraufbereitung geeigneten Katalysator zur Entfernung von Schwefelwasserstoff zu entwickeln, hinsichtlich verschiedener Verfahrensparameter und relevanter Randbedingungen durch systematische Batch- und Säulenversuche zu erproben und zu optimieren. Wichtige Kriterien zur Charakterisierung der Katalysatoren waren die Kinetik des Sulfidumsatzes, die Langzeitstabilität und die Zusammensetzung der Reaktionsprodukte. Die Nachahmung natürlich vorkommender Strukturen (z. B. Häm-Gruppe) und deren Anpassung an eine katalytische Sulfidoxidation war der Grundgedanke am Anfang der Arbeit. Entsprechende Materialien, organische Metallkomplexe (Porphyrine) auf Kohlenstoffträgern (Acetylen Black), wurden bereits erfolgreich bei der Sauerstoffreduktion in Brennstoffzellen eingesetzt. Cobalttetraphenylporphyrin (CoTPP) zeigte von allen getesteten Materialien die beste katalytische Wirksamkeit zur Sulfidoxidation. Die Sulfidumsetzung lief sowohl bei höheren pH-Werten als auch mit zunehmender Temperatur schneller ab. Anhand von Untersuchungen zum Einfluss des pH-Werts konnte bestätigt werden, dass eine katalytische Wirksamkeit nur für die Oxidation der Sulfid-Spezies HS- und S2- besteht. Mit Aktivkohle konnte ebenfalls eine katalytische Sulfidumsetzung erzielt werden, jedoch lag die Aktivität hier im Vergleich zum CoTPP deutlich niedriger. Bei allen getesteten katalytisch wirksamen Materialien entstand als vorrangiges Reaktionsprodukt Schwefel, gebildete Schwefel-Sauerstoff-Verbindungen wie Sulfat und Thiosulfat waren von untergeordneter Bedeutung. Die Untersuchungen zeigten, dass Acetylen Black aufgrund der sehr geringen Teilchengröße technisch kaum einsetzbar ist, weshalb weitere Trägermaterialien erprobt wurden. Im Gegensatz zu Aktivkohle oder Anthrazit erwiesen sich Weichfilze, insbesondere der Sigratherm Kohlenstoff-Weichfilz (KFA-Filz), als sehr gut geeignete Trägermaterialien. Beim Einsatz von Aktivkohle lagerte sich der gebildete Schwefel in den Porenräumen ab, was zu einer erheblichen Verringerung der katalytischen Aktivität führte. Dagegen wurde unter Verwendung des modifizierten Filzmaterials auch bei sehr langen Laufzeiten (bis 3000 Stunden) keine Abnahme der katalytischen Wirksamkeit beobachtet. Durch diese Katalysatormatrix konnte somit die Deaktivierung des Katalysators durch elementaren Schwefel verhindert werden. Bei abschließenden Versuchen unter Verwendung einer kleintechnischen Versuchsanlage konnte gezeigt werden, dass der Katalysator für den großtechnischen Einsatz geeignet ist. Im Vergleich zur Aktivkohle sind zwar größere Investitionskosten notwendig, andererseits können mit dem CoTPP-Material deutlich längere Laufzeiten realisiert werden. Aufgrund seiner guten technischen Handhabbarkeit ist der modifizierte KFA-Filz sowohl in kleinen dezentralen Anlagen (ländliche Siedlungen) als auch in größeren Wasserwerken einsetzbar. Zusätzliche Chemikalien sind für den Betrieb eines solchen Filters nicht erforderlich. Eine weitere Verbesserung der Sulfidentfernung wird bei langen Filterlaufzeiten durch sulfidoxidierende Bakterien bewirkt. Das Ziel, einen effizienten, technisch einsetzbaren Katalysator zur oxidativen Sulfidentfernung aus Wässern zu entwickeln, wurde somit erreicht. / Hydrogen sulfide often occurs in groundwater of arid areas. Because of its malodour, H2S containing water cannot be used as drinking water without treatment. Aeration as the most common treatment technique is less effective and leads to nasty odour of ambient air. Catalytic oxidation could be an alternative. The aim of this work was to develop and to optimize a technically applicable oxidation catalyst as well as to test its applicability under practical conditions. Various N4-chelates (e. g. porphyrins), which are frequently used for the reduction of oxygen in fuel cells, were evaluated for catalytic oxidation of sulfide at selected boundary conditions and process parameters using batch and column experiments. The new catalysts should be characterized in comparison with other materials. The oxidation kinetics, the long-time stability of the catalyst and the composition of oxidation products were the main criteria used for catalyst assessment. Cobalt tetraphenylporphyrin (CoTPP) showed the highest catalytic activity of all tested materials. The rate of sulfide transformation increased significantly with increasing temperature and at pH values higher than 6. A catalyst suitable for technical use in fixed-bed reactors was obtained by coating of a supporting material (carbon felt KFA) with the active substance. For all investigated materials, sulfur was found to be the main reaction product of the sulfide oxidation. In contrast to activated carbon, which showed catalytic activity for sulfide oxidation too, modified KFA felt materials were not blocked and deactivated by formed sulfur, even after long-term use. The new catalyst is well qualified for a stable oxidation of sulfide in water. In comparison to activated carbon, higher investment costs are required, but the carbon felt supported porphyrin has a significant longer lifetime. Because of its easy use, modified KFA felt is applicable both in small local plants and in large waterworks. There is no necessity to add chemicals or to install complex control equipment. As a positive side-effect, further improvement of sulfide elimination caused by sulfide-oxidizing bacteria was found during long filter run times.

In ariden Gebieten tritt Schwefelwasserstoff häufig im Grundwasser auf, wodurch dessen Nutzung für die Trinkwassergewinnung aufgrund des störenden Geruchs und Geschmacks stark beeinträchtigt wird. Die in der Praxis oft eingesetzte Belüftung erweist sich zumeist als ineffizient und führt zu Geruchsbelästigungen in der Umgebungsluft. Das Ziel der Arbeit, die im Rahmen eines deutsch-israelischen Forschungsprojekts angefertigt wurde, bestand darin, einen wirksamen und für den praktischen Einsatz bei der Wasseraufbereitung geeigneten Katalysator zur Entfernung von Schwefelwasserstoff zu entwickeln, hinsichtlich verschiedener Verfahrensparameter und relevanter Randbedingungen durch systematische Batch- und Säulenversuche zu erproben und zu optimieren. Wichtige Kriterien zur Charakterisierung der Katalysatoren waren die Kinetik des Sulfidumsatzes, die Langzeitstabilität und die Zusammensetzung der Reaktionsprodukte. Die Nachahmung natürlich vorkommender Strukturen (z. B. Häm-Gruppe) und deren Anpassung an eine katalytische Sulfidoxidation war der Grundgedanke am Anfang der Arbeit. Entsprechende Materialien, organische Metallkomplexe (Porphyrine) auf Kohlenstoffträgern (Acetylen Black), wurden bereits erfolgreich bei der Sauerstoffreduktion in Brennstoffzellen eingesetzt. Cobalttetraphenylporphyrin (CoTPP) zeigte von allen getesteten Materialien die beste katalytische Wirksamkeit zur Sulfidoxidation. Die Sulfidumsetzung lief sowohl bei höheren pH-Werten als auch mit zunehmender Temperatur schneller ab. Anhand von Untersuchungen zum Einfluss des pH-Werts konnte bestätigt werden, dass eine katalytische Wirksamkeit nur für die Oxidation der Sulfid-Spezies HS- und S2- besteht. Mit Aktivkohle konnte ebenfalls eine katalytische Sulfidumsetzung erzielt werden, jedoch lag die Aktivität hier im Vergleich zum CoTPP deutlich niedriger. Bei allen getesteten katalytisch wirksamen Materialien entstand als vorrangiges Reaktionsprodukt Schwefel, gebildete Schwefel-Sauerstoff-Verbindungen wie Sulfat und Thiosulfat waren von untergeordneter Bedeutung. Die Untersuchungen zeigten, dass Acetylen Black aufgrund der sehr geringen Teilchengröße technisch kaum einsetzbar ist, weshalb weitere Trägermaterialien erprobt wurden. Im Gegensatz zu Aktivkohle oder Anthrazit erwiesen sich Weichfilze, insbesondere der Sigratherm Kohlenstoff-Weichfilz (KFA-Filz), als sehr gut geeignete Trägermaterialien. Beim Einsatz von Aktivkohle lagerte sich der gebildete Schwefel in den Porenräumen ab, was zu einer erheblichen Verringerung der katalytischen Aktivität führte. Dagegen wurde unter Verwendung des modifizierten Filzmaterials auch bei sehr langen Laufzeiten (bis 3000 Stunden) keine Abnahme der katalytischen Wirksamkeit beobachtet. Durch diese Katalysatormatrix konnte somit die Deaktivierung des Katalysators durch elementaren Schwefel verhindert werden. Bei abschließenden Versuchen unter Verwendung einer kleintechnischen Versuchsanlage konnte gezeigt werden, dass der Katalysator für den großtechnischen Einsatz geeignet ist. Im Vergleich zur Aktivkohle sind zwar größere Investitionskosten notwendig, andererseits können mit dem CoTPP-Material deutlich längere Laufzeiten realisiert werden. Aufgrund seiner guten technischen Handhabbarkeit ist der modifizierte KFA-Filz sowohl in kleinen dezentralen Anlagen (ländliche Siedlungen) als auch in größeren Wasserwerken einsetzbar. Zusätzliche Chemikalien sind für den Betrieb eines solchen Filters nicht erforderlich. Eine weitere Verbesserung der Sulfidentfernung wird bei langen Filterlaufzeiten durch sulfidoxidierende Bakterien bewirkt. Das Ziel, einen effizienten, technisch einsetzbaren Katalysator zur oxidativen Sulfidentfernung aus Wässern zu entwickeln, wurde somit erreicht. / Hydrogen sulfide often occurs in groundwater of arid areas. Because of its malodour, H2S containing water cannot be used as drinking water without treatment. Aeration as the most common treatment technique is less effective and leads to nasty odour of ambient air. Catalytic oxidation could be an alternative. The aim of this work was to develop and to optimize a technically applicable oxidation catalyst as well as to test its applicability under practical conditions. Various N4-chelates (e. g. porphyrins), which are frequently used for the reduction of oxygen in fuel cells, were evaluated for catalytic oxidation of sulfide at selected boundary conditions and process parameters using batch and column experiments. The new catalysts should be characterized in comparison with other materials. The oxidation kinetics, the long-time stability of the catalyst and the composition of oxidation products were the main criteria used for catalyst assessment. Cobalt tetraphenylporphyrin (CoTPP) showed the highest catalytic activity of all tested materials. The rate of sulfide transformation increased significantly with increasing temperature and at pH values higher than 6. A catalyst suitable for technical use in fixed-bed reactors was obtained by coating of a supporting material (carbon felt KFA) with the active substance. For all investigated materials, sulfur was found to be the main reaction product of the sulfide oxidation. In contrast to activated carbon, which showed catalytic activity for sulfide oxidation too, modified KFA felt materials were not blocked and deactivated by formed sulfur, even after long-term use. The new catalyst is well qualified for a stable oxidation of sulfide in water. In comparison to activated carbon, higher investment costs are required, but the carbon felt supported porphyrin has a significant longer lifetime. Because of its easy use, modified KFA felt is applicable both in small local plants and in large waterworks. There is no necessity to add chemicals or to install complex control equipment. As a positive side-effect, further improvement of sulfide elimination caused by sulfide-oxidizing bacteria was found during long filter run times.

Catalytic oxidation plays a crucial role in current chemical and pharmaceutical industries which is also a leading technology for green chemical processes. In Nature, the ubiquitous cytochrome P450 enzymes can catalyze a wide variety of oxidation reactions with high efficiency and selectivity. Many transition metal catalysts are designed as the biomimetic model of cytochrome P450 enzymes. In this work, series of metalloporphyrins and metallocorroles have been successfully synthesized to investigate and develop catalytic selective oxidation of sulfides to sulfoxides. Manganese(III) porphyrin complexes (2) and manganese(III) corrole complexes (6) with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source exhibited remarkable catalytic activity toward selective oxidation of sulfides to sulfoxides under mild conditions. Conspicuous is the fact that readily soluble PhI(OAc)2 in the presence of a small amount of water is more efficient than the commonly used PhIO and other oxygen sources under identical conditions. It was found that the reactivity of manganese(III) porphyrin catalysts was greatly affected by axial ligand and the weakly binding chlorate gave the highest catalytic activity in the oxidation of sulfide. Both porphyrin-manganese and corrole-manganese catalysts catalyzed the highly selective oxidation of para-substituted thioanisoles with PhI(OAc)2 in the presence of a small amount of water. Complete conversion and of sulfide and excellent selectivities for sulfoxide were achieved within 120 min. We discovered that photo-disproportionation of a bis-porphyrin-diruthenium(IV)- μ-oxo dimer gave a porphyrin-ruthenium(III) species and a putative poprhyrinruthenium( V)-oxo species that can be detected and studied in real time using laser flash photolysis methods. As determined by its spectral and kinetic behavior, the same oxo transient was also formed by photolysis of a porphyrin-ruthenium(III) N-oxide adduct. Second-order rate constants for reactions with several substrates at 22 °C were determined; representative values of rate constants were kox = 6.6 × 103 M-1 s-1 for diphenylmethanol, kox = 2.5 × 103 M-1 s-1 for styrene, and kox = 1.8 × 103 M-1 s-1 for cyclohexene.

The aim of the project described in this thesis is to synthesise new functional molecules which interact with light for neurophysiological applications. In particular, I describe a family of amphiphilic porphyrins with large first hyperpolarisabilities which are used as SHG contrast agents and voltage-sensitive probes. In addition I detail a methodological microscopy tool and a novel caged form of a neuronal ion-channel antagonist. Chapter 1 introduces the key concepts underlying the use of dyes as SHG contrast agents. In particular it focuses on aspects of molecular design, covering both the amphiphilicity and nolinearity required by the target molecule. It covers quantification of the nonlinear properties of SHG stains, then surveys a number of examples which showcase the flexibility of SHG imaging as a biomedical technique. Chapter 2 describes a family of amphiphilic porphyrins with large first hyperpolarisabilities. Working from the structure-property relationships identified in Chapter 1, we fully characterise these dyes and demonstrate that they can be used in SHG imaging. We demonstrate that these molecules may also be tuned by complexation of a metal ion which can modulate their photophysical and solubility behaviour. Chapter 3 provides a description of how to determine the orientational distribution of dipolar dyes in a membrane by multiphoton microscopy. We measure the signal intensity of the dye in a model membrane system then find distributional moments which lead to the distribution itself. Chapter 4 explores whether off-axis contributions to the first hyperpolarisability tensor can significantly augment the dominant on-axis contribution from the main dipolar charge-transfer band. We synthesise and characterise a series of cis-donor cis-acceptor porphyrin compounds and explore their biophysical characteristics. Chapter 5 is the culmination of this project and after discussing method development, goes on to show how we measure the voltage sensitivity of an amphiphilic porphyrin SHG dye. We compare the archetypal porphyrin dye chromophore with three commercially available styryl dyes and demonstrate that our dye has greater sensitivity and a more rapid response. Chapter 6 describes a side project, the use of a photolabile cage to protect MK801, a neuronal ion-channel antagonist. By developing a water soluble photolabile cage using molecular design techniques, we are able to release MK801 in neurons with precise spatiotemporal control, allowing us to pinpoint the locus of two key neurophysiological processes.

The third-order nonlinear optical (NLO) properties of indium tin oxide (ITO) thin films, Fe3+, Mn3+, Co2+ 5,10,15,20-tetrakis-4hydroxytetraphenyl)porphyrin (TPP) films, and a series of ethynyl-linked azobenzene oligomers were investigated using degenerate four wave mixing (DFWM) with 100 fs laser pulses. To measure the NLO of ITO thin films, A DFWM method for measuring thin films on thick substrates was refined for the characterization of films less than 100 nm thick and applied to ITO films ~25 nm thick. It was found that the third-order nonlinear susceptibility of ITO, χ(3)ITO, is purely electronic at 900 - 1300 nm (11000 - 7700 cm-1) and has a value of (2.16 ± 0.18) x 10-l8 m2 V-2. The χ(3)IT0 value reaches (3.36 ± 0.28) x 10-l8 m2 V(sup>-2 at 1500 nm (6700 cm-1) due to two-photon absorption by free carriers (electrons). Ultrafast electron relaxation was also observed. The ~100 fs lifetime of this process could reflect electron scattering in the conduction band. This DFWM method was also used to investigate the two-photon properties of ~500 nm thick electropolymerized films of Fe3+, Mn3+, and Co2+ TPP in the near-IR spectral region. Metalloporphyrins with strong charge transfer (CT) transitions inthe linear absorption spectra also show enhanced two-photon absorption. (Metalloporphyrin two-photon absorption cross section, δ, increases >10 times over that for the metal free porphyrin.) This effect was attributed to a two-photon induced charge transfer between the metal ion's d orbitals and the π-system of the porphyrin. Correlationof one- and two-photon absorption properties of transition metal porphyrins suggests a new and simple approach to improve organic materials for photonic applications. Finally, a series of oligomers consisting of ethynyl-linked azobenzene units was prepared using Pd-catalyzed cross coupling. The linear and nonlinear optical properties of the oligomers were investigated. The molecular second hyperpolarizability, γ, followed the power law γσ n2.12±0.05 (n is number of repeat units) for unusually large molecular lengths. The exceptional exciton delocalization length exceeds 360 conjugated bonds (>49 nm) and is attributed to the rigidity of the conjugated backbone.

Title: Methods of Study of Photosensitizer-photophysics with Application on Thiazolyl-porphyrins Author: Marek Scholz Department: Department of Chemical Physics and Optics Supervisor: RNDr. Roman Dědic, Ph.D. Supervisor's e-mail address: Roman.Dedic@mff.cuni.cz Abstract: Photodynamic therapy for oncologic and various chronic diseases is a rapidly emerging method of treatment. It is based on the production of highly reactive singlet oxygen and free radicals by excitation energy transfer from the molecules of photosensitizers. Photosensitizers are preferentially accumulated in the target tissues and locally illuminated. This way produced reactive species cause apoptosis or necrosis of the cells leading to the desired therapeutic effect. Synthesis and subsequent photophysical characterization of photosensitizing dyes is a fundamental part of the development of photodynamic methods. The main aim of the work is to explain the most widely used methods of photophysical study of photosensitizers and apply them to new synthesized photosensitizers: thiazolyl-porphyrins. Methods of absorption and fluorescence spectroscopy, flash- photolysis, time- and spectral-resolved detection of luminescence, optoacoustic spectroscopy and other spectroscopic methods were used. Thiazolyl-porphyrins proved to be promising new...

Photodynamic therapy (PDT) is a treatment modality for cancer. It combines selective accumulation of chemical compounds, called photosensitizers (PS), with light to irreversibly damage cancer cells via oxidative stress. The main goal of this thesis was to study photosensitizers represented by a unique group of newly synthesized porphyrin derivatives with glycol chain substitution. Glycol-functionalized porphyrins containing one to four low molecular weight glycol chains that are linked via ether bonds to the meta-phenyl positions of meso-tetraphenylporphyrin (mTPP(EG)1-4) were compared with fluorinated (pTPPF(EG)4) and nonfluorinated (TPP(EG)4) derivatives having glycol chains in para-phenyl positions. The cellular uptake and photodynamic activity was significantly dependent on terminal groups of the glycol substituent. Hydroxy glycol porphyrins, in contrast with methoxy glycol porphyrins, exhibited efficient intracellular transport and high induction of apoptosis in tumor cell lines in vitro. After initial testing effective prototype hydroxy ethylene glycol derivatives were selected and analyzed in detail. Para derivatives pTPP(EG)4 and pTPPF(EG)4 accumulated mainly in lysosomes whereas meta derivatives mTPP(EG)1-4 in the endoplasmic reticulum (ER). Position of ethylene glycol chain on the...

Devido à sua intensa absorção de luz na região visível do espectro, as porfirinas e seus derivados (clorinas e bacterioclorinas) são de grande importância na terapia fotodinâmica (TFD) para o tratamento de doenças neoplásicas. Neste trabalho foram sintetizadas as novas vinil-porfirinas estrategicamente funcionalizadas (47 e 48), seguida de uma sistemática de reações de Diels-Alder com dieófilos ativados, com o propósito de obter clorinas e/ou bacterioclorinas para potenciais aplicações em TFD. / Due to their strong absorption in the visible region, porphyrins and related derivatives (chlorins and bacteriochlorins) are very important in photodynamic therapy (PDT) for the treatment of neoplasic diseases. In this work were synthesized the novel and strategically functionalizated vinyl-porphyrins 47 and 48, followed by systematic Diels-Alder reactions with activated dienophiles to obtain chlorins and/or bacteriochlorins, potentially useful on PDT.

Neste trabalho são descritas as propriedades morfológicas, condutoras, fotoeletroquímicas e eletrocatalíticas de filmes de porfirinas supramoleculares, contendo complexos de rutênio polipiridina e clusters trinucleares de rutênio. Foram empregadas técnicas de microscopia de varredura por sonda, voltametria cíclica, espectroscopia de impedância eletroquímica, espectroeletroquímica UV-vis, voltametria de disco rotatório e experimentos combinados de eletroquímica/fotoeletroquímica. Cálculos semi-empíricos foram utilizados em alguns casos para dar maior suporte às interpretações. O método de preparação dos filmes tem efeito drástico sobre o tipo de empacotamento do material. Conseqüentemente, as propriedades condutoras e fotoeletroquímicas também são afetadas. Por exemplo, o coeficiente de difusão eletrônica (DeCm2) pode variar até 104 vezes dependendo do tipo de empacotamento de uma mesma porfirina utilizada. Os processos de condução desses filmes são controlados por um mecanismo redox envolvendo os sítios de rutênio e são mediados por orbitais &#906;* dos anéis porfirínicos e polipiridínicos. A intensidade de fotocorrente em função do &#955; incidente depende do mecanismo de transporte de elétrons e pode ser modulada pela natureza e grau de acoplamento eletrônico entre os anéis porfirínicos dentro do filme. Esses filmes exibem propriedades eletrocatalíticas na oxidação de substratos de interesse ambiental, da indústria alimentícia e do setor médico, tais como nitrito, sulfito e ácido ascórbico. As eficiências desses materiais são altas, com kf > 104 mol-1dm3s-1. Em catalisadores redox foi verificada uma tendência exponencial entre a constante cinética de transferência eletrônica heterogênea e potencial de E1/2 do centro redox no filme, como previsto pela equação de Marcus. A cobalto porfirina contendo quatro clusters trinucleares de rutênio se comporta como um eficiente catalisador molecular da redução do O2 por 4 elétrons, em pH < 5. O mecanismo de redução não envolve a bis-coordenação do O2 a dois sítios metálicos. Nesse caso, efeitos eletrônicos dos complexos periféricos devem ativar o centro da metaloporfirina, promovendo a transferência multieletrônica e prevenindo a formação de espécies reativas, como OH· e O2-. Uma célula de FIA foi construída visando a análise quantitativa de sulfito, exibindo alta eficiência em termos de limite de detecção, freqüência de análises e reprodutibilidade. O sistema FIA foi adaptado e empregado juntamente com o filme de uma porfirina supramolecular para reproduzir as funções básicas de um portal lógico, exibindo comportamento singular, podendo desempenhar as três funções (AND, OR e NOT) num único sistema químico integrado. / A full characterization of the morphologic, conduction, photoelectrochemical and electrocatalytic properties of supramolecular porphyrin films containing ruthenium polypyridyl or ruthenium clusters, is described. Techniques, such as scanning probe microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, UV-vis spectroelectrochemistry, rotating disk electrode voltammetry, and combined electrochemical/photoelectrochemical experiments were employed. Semi-empirical calculations were utilized in order to obtain more information on the interpretations. The preparation method of film deposition has a special effect on the material packing. Consequently, the conduction and photoelectrochemical properties are also affected. For example, the electronic diffusion coefficient (DeCm2) differs by up to 104 times depending on the packing characteristics of the same porphyrin material. The conduction process is limited by a redox mechanism involving the ruthenium centers and is mediated by &#960;* orbitals of the porphyrin or polypyridine species. The photocurrent intensity as a function of the incident &#955; depends on the electron transport mechanism involved and this can be tuned by the nature and the degree of electronic coupling between the porphyrin rings, in the film. This kind of films also exhibits electrocatalytic activities for the oxidation of substrates with interests in the environmental, food and medical areas, such as nitrite, sulfite, and ascorbic acid. The efficiency of these materials are also high, with kf > 104 mol-1dm3s-1. An exponential relationship of the heterogeneous electron transfer kinetic constant with the E1/2 of the redox center was found, as predicted by the Marcus equation. The cobalt porphyrin containing four ruthenium clusters behaves as an efficient catalyst for the 4-electron reduction of O2, at pH <5. The mechanism does not involve the bis-coordination of O2 to two metallic centers, but electronic effects from the ruthenium clusters should be activating the metalloporphyrin center, promoting the multi-electronic transfer and preventing the formation of reactive species, such as OH· e O2-. A FIA cell was built in order to provide a quantitative analysis of sulfite, and it exhibited high sampling frequency, reproducibility, as confirmed by the low detection limit (0.1 &#181;mol.dm-3). The FIA system was adapted and employed with a supramolecular porphyrin film as logic gates and they exhibited a unique behavior, operating the three basic functions (AND, OR and NOT) in a single integrated chemical system.